Chemical manufacture



March 1950 M. DE GRooTE ETAL CHEMICAL MANUFACTURE 2 shuts-sheet 1 Filed Feb. 1S, 1948 MELVIN DE ojozmIn-IZOZ INVENTOR GROOTE AND ERNHARD KEISER BY B Willi L. @mult ATTORNEY Patented Mar. 7, 1950 2,499,365 CHEMICAL MANFACTURE Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware Application February 16, 1948, Serial No. 8,722 In Venezuela March 7, 1947 9 Claims. l

This invention relates to processes and procedures particularly adapted for preventing, breaking, or resolving emulsions of the waterin-oil type, and particularly petroleum emulsions. This application is a continuation-in-part of copending applications Serial Nos. 518,660 and 518,661, illed January 17, 1944; Serial Nos. 666,816, 666,817, 666,818 and 666,821, led May 2, 1946; Serial Nos. 727,282 and 727,283, led February 7, 1947;'and Serial Nos. 751,605, 751,610, 751,611 and 751,612, iiled May 31, 1947, all now abandoned.

New chemical products or compounds, as well as the application of such chemical compounds, products, and the like, in various other arts and industries, along with methods for manufacturing said new chemical products or compounds which are of outstanding value in demulsication described herein are described and claimed in co-pending applications, Serial Nos. 751,611, 751,612, 751,620 and 751,623, led May 31, 1947, all now abandoned.

Our invention provides an economical and A rapid process for resolving petroleum emulsions ofthe water-in-oil type that are commonly re-' tion and subsequent demulsiiication under the` fusible, organic solvent-soluble, water-insoluble resins, on oxyalkylation, and specifically, oxyethylation, yield products of unusual value for demulsifcation purposes provided that oxyalkylation is continued to the degree that hydrophile properties are imparted to the compound.

By "oxyalkylation-susceptible" we mean that the resin is capable of reacting with an alkylene oxide so that an alkyleneoxy radical or radicals is or are introduced into the resin molecule. Generally speaking, such reactive or labile hydrogen atoms are attached to nitrogen, oxygen, or sulfur, usually nitrogen or oxygen, as in resins having phenolic hydroxyl groups, amine or amido groups with nitrogen-linked hydrogen, alcoholiform hydroxyl groups, carboxy groups, or the like. There are some resins susceptible to oxyalkylation because of the presence of reactive ester radicals, as in certain products derived from olive oil. In any event, the resins used for the preparation of the products used in accordance with the invention must be capable of reaction with an alkylene oxide of the type hereinafter specified with introduction of oxyalkylene groups into the resin molecule.

By fusible," we do not mean that the resin is thermoplastic in the sense in which that term is ordinarily applied to resins, namely, as identifying products which can be heated repeatedly without losing thermoplasticity but rather that the resin is suiliciently fusible to permit processing to produce the oxyalkylated products without giving insoluble materials or causing insolubilization or gel formation or .rubberness In other words the products must be capable of being melted or softened by heat'but the fact that they may not be capable of repeated fusing is not sufficient to warrant rejection for use as intermediates.

The term solvent-soluble we use to differentiate between useful resins which are soluble -in atleast one of the large number of organic solvents which are available, and to indicate that the resin consists of separate molecules. as distinguished from resins which are soluble in no solvent, any fragment of which is regarded as consisting of substantially a single molecule. It is not necessary that the resin be soluble in more than one of the available solvents, as what is here involved is the essential structural characteristic of the resin, that is, that it consist We use the term"waterinsoluble" to exclude` those resins which are water-soluble, or have no appreciable hydrophile properties, in other yvords, to exclude such water-soluble resins as are produced from resorcinol, for example, for use as adhesives. The term does not exclude resins which are. water-insoluble but soluble in aqueous alkali or aqueous acid, for example, certain salicylic acid and amine-derived resins.

Attention -is directed to thirteen co-pending applications:

(1) In respect to the use as demulsifying agents of oxyalkylated 2,4,6 hydrocarbon-substituted phenol-aldehyde resins with the proviso that the'hydrocarbon substituent in the phenolic nucleus has 4 to 8 carbon atoms, we refer to our co-pending application for patent, Serial No. 727,282, filed February 7, 1947 (abandoned).

(2) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsiiication, we refer to our co-pending application, Serial No. 751,619, filed May 31, 1947 (abandoned).

(3) In respect to the use as demulsifying agents of oxyalkylated 2,4,6 hydrocarbon-substituted phenol-aldehyde resins with the proviso that the hydrocarbon substituent in the phenolic nucleus has 9 to 18 carbon atoms, we refer to our co-pending application, Serial No. 751,608, filed May 31, 1947 (abandoned).

(4) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsication, we refer to our co-pending application, Serial No. 751,618, led May 3l, 1947 (abandoned).

(5) In respect to the use as demulsifying agents of oxyalkylated 2,4,6 hydrocarbon-substituted phenol-aldehyde resins with the proviso that the hydrocarbon substituent in the phenolic nucleus has at least 2 and not moreA than 3 carbon atoms, we refer to our` co-pending application for patent, Serial No. 751,606, filed May 31, 1947 (abandoned).

(6) In respect to the same; products as new compositions or as new products valuable for various purposes in addition to demulsiiication, we refer to our co-pending application, Serial No. 751,617, led May 31, 1947 (abandoned).

(7) In respect to the use as demulsifying agents of oxyalkylated 2,4,8 hydrocarbon-substituted phenol-aldehyde resins with the proviso that the hydrocarbon substituent have 1 to 24 carbon atoms, we refer to our co-pending application, Serial No. 751,610, filed May 31, 1947 (abandoned) 1 (8) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsication, we refer to our co-pending application, Serial No. 751,623, filed May 31, 1947 (abandoned).

(9) In respect to the use as demulsifying agents of oxyalkylated 2,4,6 hydrocarbon-substituted phenol-aldehyde resins with the proviso that the hydrocarbon substituent in the phenolic nucleus has at least 2 and not'more than 24 carbon atoms, particularly derivatives of mixed resins in which phenols. having 4 to 8 carbon atoms in the substituent position, are mixed with phenols having 2 to 3 or 9 to 24 carbon atoms,

we refer to our co-pending application, Serial No. 8,728, filed February 16, 1948.

(10) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsiflcation, we refer to our co-pending application Serial No. 8,729, nled February 16, 1948.

(1l) In respect to the use as demulsifying agents of oxyalkylated 2,4,6 substituted phenolaldehyde resins without limitation of the nature of the substituent which renders the phenol difunctional (for instance, itmay be chlorine or may be a radical containing oxygen or nitrogen in addition to carbon and hydrogen) we refer to our co-pending application, Serial No. 8,724, filed February 16, 1948.

(l2) In'respect to the same products as new compositions or new products valuable for various processes in addition to demulsiiication, attention is directed to our co-pending application, Serial N0. 8,725, led February 16, 1948.

(13) In respect to the use as demulsifying agents of oxyalkylated phenolic resins, generally, we refer to our application Serial No. 8,723, iiled February 16, 1948.

The present invention involves the use, as a demulsifler, of a hydrophile product resulting from the oxyalkylation of an oxyalkylationsusceptible, fusible, organic solvent-soluble,water insoluble resin in whichthe number of introduced oxyalkylene groups is suicient to impart to the product hydrophile properties, that is, to to make it sub-surface-active or surface-active as those terms are hereinafter defined, the alkylene radicals of the oxyalkylene groups being ethylene, propylene, butylene, hydroxypropylene or hydroxybutylene corresponding to the alphabeta-alkylene oxides, ethylene oxide, alpha-betapropylene oxide, alpha-beta-butylene oxide, glycide and methyl glycide. The number of oxyalkylene groups introduced is at least twice the number of structural units of the resin; and the radicals so introduced are indicated by the formula (ROML in which n is a number from 1 to 20 and is statistically taken.

Included among the resins which are suitable for the preparation of the products used in the practice of the invention, all of which must conform to the requirements set forth above, are phenol-aldehyde resins, phenol-sulfur resins, phenol-acetylene resins, including resins produced from phenol and substituted phenols, ncluding difunctional, trifunctional and tetrafunctional phenols, naphthols, bisphenols, salcylic acid and salicylates, etc., modified phenolic resins, including phenol-terpene resins, phenolterpene-aldehyde resins, phenol-naphthalenealdehyde resins, phenol-urea-formaldehyde resins, phenol-aniline-formaldehyde resins, phenolglycerol resins, etc., non-phenolic resins having the necessary labile or reactive hydrogen including urea and substituted urea-aldehyde resins, sulfonamide-aldehyde resins, polycarboxy-polyamine resins, polyester resins, resins derived by ring hydrogenation of phenolic resins, and the like. Our experience, based upon very extensive investigation, is that the oxyalkylation of any resin conforming to the requirements set forth above gives an eflicient demulsifying agent, providing only that the oxyalkylation is carried to an extent such that the product has hydrophile properties, that is, the product has emulsifying properties or is self-emulslflable or self-dispersible or more hydrophile, e. g., water-soluble, and providing the product does not become rubbery and non-hydrophilic, presumably as a result of cross-linking or the like, during the oxyalkylatlon. Naturally, some products are more eicient than others, and indeed, the relative eiliciency of the materials may vary from emulsion to emulsion, but we have found no hydrophilic oxyalkylated product from an oxyalkylation-susceptible, fusible, organic-solvent-soluble, water-insoluble resin which was not effective for demulsifyng purposes.

More particularly, the present invention involves the use as a demulsier of a compound having the following characteristics:

(1) Essentially a polymer, usually and advantageously linear, but not necessarily so, having at least 3 and preferably not over 15 or 20 structural units. It may have more.

(2) The parent resin polymer being fusible and organic solvent-soluble as hereinafter described.

(3) The parent resin polymer being free from cross-linking or structure which cross-links during the heating incident to the oxyalkylation procedure to an extent suiiicient to prevent the possession of hydrophile or subsurface-active or surface-active properties by the oxyalkylated resin.

(4) Each alkyleneoxy group is introduced at a point in the resin structure where there is a reactive hydrogen atom or some other point of reactivity. If the resin is phenolic, alkyleneoxy groups are introduced at the phenolic hydroxyl positions.

(5) The total number of alkyleneoxy radicals introduced must be at least sufficient to introduce hydrophile properties, i. e., sumcient to endow the product with suicient hydrophile property to have emulsifying properties, or be self-emulsir'iable or self-dispersible or the equivalent as hereinafter described; and must be at least equal to twice the number of structural units lin the resin. The invention is concerned particularly with the use of sub-surface-active and surfaceactive compounds.

(6) The parent resin must be water-insoluble.

In this specication and in the appended claims,-

reference is made to resins having structural units. It is well known that resins are formed by reaction of a polyfunctional (di, tri, tetra-, etc.) material with a material (also polyiunctional) which supplies a bridging or a linking radical, or by polymerization (homoor hetero) or by a combination of the two. Thus, in the production of most phenol-aldehyde resins, the phenol, whether trifunctional as with phenol, difunctional, as with paratertiary-butyl phenol, or tetrafunctional, as with certain bis-phenols, serves as a polyfunctional material and the aldehyde serves to supply bridging methylene radicals. The same is true of such resins as the ureaaldehyde resins. With such resins as these, the identification of the structural units is simple; they are the units or nuclei of the polyfunctional material with, except in the case of the terminal nuclei, a bridging radical attached thereto.

Similarly, identification is simple in the case of homo-polymers, as, for example, vinyl phenol resins, where each vinyl phenol nucleus represents a structural unit.

With such resins as the dicarboXy-diamine resins, e. g., the nylon-type resin. identification materials is to be regarded as the polyfunctional resinogen and which the material which supplies the bridging radical, but, for practical purposes, from the standpoint of the present invention, this is unimportant, as either may be regarded as the bridging radical with the other as the polyfunctional resinogen and the structural unit considered to be either one, with the other being the associated bridging radical.

With modified phenol resins, such as phenolnaphthalene-aldehyde resins, or terpene-phenolaldehyde-resins, or phenol-ureo-aldehyde-resins, theidentication of the structural unit must necessarily be arbitrary again, but for purposes of definition of the term as used in the present application, it will be defined in instances such as this as a combination of the nuclei of two of the reactants, that is, the residue formed when two of the initial reacting molecules have combined, for example, one terpene and one phenol molecule, or one phenol and one aldehyde molecule, or one urea and one formaldehyde molecule, or one cumarone and one indene molecule, or one cumarone and one phenol molecule, or one rosin and one phenol molecule, etc.

Thus, generally stated, the term structural unit, as herein used to designate what may be regarded as the resin segments or building blocks or repeating units or recurring units of the resins, means the residue remaining after the combination of two molecular units of the resinforming materials which are reacted to form the ultimate resin, each representing the nucleus or residue of a polyfunctional compound. In phenol aldehyde resins the unit is a phenolic group plus the methylene-bridging group; in polyester resins, the acid residue plus the alcohol residue; in modified phenol-aldehyde resins the phenolic group plus the aldehyde residue or the phenolic group plus the modifying radical or the modifying radical plus the aldehyde radical; in homopolymers such as that derived from vinyl phenol, the residue of a single molecule of the material polymerized; in urea-formaldehyde-phenol resins, either the phenol group plus the aldehyde group or the urea group plus the aldehyde group; in polycarboxy-polyamine resins, one polycarboxy residue plus one polyamine residue; in polyester resins, one polyacid residue plus one polyalcohol residue, etc. In many resins produced from two or more reactants, for example, a difunctional phenol plus an aldehyde, there will be one terminal structural unit (in some cases more than one) which lacks the bridging radical, but is nevertheless to be regarded as a structural unit.

We have also found that the remarkable properties of the present materials as demulsiers persist in derivatives which bear a simple genetic relationship to the parent materials, and in fact to the ultimate resin polymer, for instance, in the products obtained by reaction of the oxyalkylated compounds with low molal monocarboxy acids, high molal monocarboxy acids, polycarboxy acids, or their anhydrides, alpha-chloro monocarboxy acids, epichlorohydrin, etc. The derivatives also preferably must be obtained from oxyalkylated products showing at least the necessary hydrophile properties per se.

For convenience, there is attached hereto a chart illustrating within obvious limitations, types of resins which are among those suitable for the production of products useful in the practice of this invention. The chart is not exhaustive.

The invention will be illustrated by the followinvolves the diiculty of deciding which of the ing specific examples, giving specific directions 7 for preparing oiwallnvlation susceptible, waterinsoluble, organic-solvent-soluble, fusible resins (Examples 1a-381a) carrying out the oxyalkylation procedure to produce products useful in the Ipractice of the invention (Examples 1b98b and I in present day practice, as hereafter described.

Example 1a Grams Para-tertiary butylphenol (1.0 mole) 150 Formaldehyde, 37% (1.0 mole) 81 Concentrated HC1 1.5

Monoalkyl (Clar-Cao, principally CirCu) benzene monosulfonic acid sodium salt-- 0.8 Xylene 100 (Examples of alkylaryl sulfonic acids which serve as catalysts and as emulsiers particularly in the form of sodium salts include the following:

KSL.

R is an alkyl hydrocarbon radical having 12-14 carbon atoms.

R is an alkyl radical having 3-12 carbon atoms and n represents the numeral 3, 2, or 1, usually 2, in such instances where R contains less than 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, We have employed a monoalkylated benzene monosulfonic acid or the sodium salt thereof wherein the alkyl group contains 10 to 14 carbn atoms. We have found equally effective and interchangeable the following specific sulfonic acids or their sodium salts: A mixture of diand tripropylated naphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid; and nonyl naphthalene monosulfonic acid.)

The equipment used was a conventional twopiece laboratory resin pot. The cover part of the equipment had four openings: one for reflux condenser; one for the stirring device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In the manipulation employed, the separatory funnel insert for adding reactants was not used. 'I'he device was equipped with a combination reux and water-trap apparatus so that the single piece of apparatus could be used as either a reflux condenser or a water trap, depending on the posiion of the three-way glass stopcock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve Without disconnecting the equipment.

structed to fit snugly around the resin pot. Such heaters, with regulators, are readily available.

The phenol, formaldehyde, acid catalyst, and solvent were combined in the resin pot above described. This particular phenol was in the form of a ilaked solid. Heat was applied with The resin pot 'was4 lheated with a glass fiber electrical heater congentle stirring and the temperature was raised to -85 C., at which point a mild exothermic reaction took place. This reaction raised the temperature to approximately 110 C. The reaction mixture was then permitted to reux at 10o-105 C. for between onek and one and one-half hours. The reflux trap arrangement was then changed from the reflux position to the normal water entrapment position. The water of solution and the water of reaction were' permitted to distill out and collect in the trap. As the water distilled out, the temperature gradually increased to approximately C. which required between 1.5 to 2 hours. At this point the water recovered in the trap, after making allowance for a small amount of water held up in the solvent. corresponded to the expected quantity. y

The solvent solution so obtained was used as such in subsequent oxyalkylation steps. We have also removed the solvent by conventional means, such as evaporation, distillation or vacuum distillation, and we customarily take a small sample of the solvent solution and evaporate the solvent to note the characteristics of the solventfree resin. The 'resin obtained in the operation above described was clear, light amber colored, hard, brittle, and had a melting point of C.

Attention is directed to the fact that tertiary butylphenol, in presence of a strong mineral acid as a catalyst and using formaldehyde, sometimes yields a resin which apparently has a very slight amount of cross-linking. Such resin is similar to the one described above except that it is somewhat opaque, and its melting point is higher than the one described above and there is a tendency to cure. Such a resin is generally dispersible in xylene but not soluble to give a clear solution. Such dispersion can be oxyalkylated in the same manner as the clear resin. If desired,

a minor proportion of another and inert solvent, such as diethyleneglycol diethylether, may be employed along with xylene, to give a clear solution prior to oxyalkylation. This fact of solubilization shows the present resin molecules are still quite small, as contrasted with the very large size of extensively cross-linked resin molecules. If following a given procedure with a given lot of the phenol, such a resin is obtained, the amount of catalyst employed is advantageously reduced slightly or the time of reflux reduced slightly, or both, or an acid such as oxalic acid is used instead of hydrochloric acid. Purely as a matter of convenience due to better solubility in xylene, we prefer to use a clear resin but if desired either type may be employed.

Example 2a 'I'he same procedure was followed as in Example 1a preceding, and the materials used the same, except that the para-tertiary butylphenol was replaced by an equal amount of para-secondary butylphenol. The phenol was a solid of a somewhat mushy appearance, resembling moist cornmeal rather than dry flakes.

is said there applies with equal force'and effect in the instant example.

The appearance of the resin was substantially identical with' MOIlOaIkyl (C10-C20, principally C12-C14) benzene monosulfonic acid sodium salt-- 0.8 Xylene 100 The procedure followed was the same as that used in Example 1a, preceding. The phenol employed was a laked solid. The solvent-free resin was dark red in color, hard, brittle, with a melting point of 12S-140 C. It was xylene-soluble.

Example 4a The phenol employed (164 grams) was parasecondary amylphenol, which is a liquid. The procedure followed was the same as that used in Example 1a, preceding. The solvent-free resin was hard and brittle, reddish-black in color and with a. melting point of 80-85 C.

'I'he phenol employed (164 grams) was a commercially available mixed amylphenol containing approximately 95 parts of para-tertiary amylphenol, and 5 parts of ortho-tertiary amylphenol. It was in the form of a fused solid. The procedure employed was the same as that used in Example 1a, preceding. The appearance of the resin was substantially the same as that of the product of Example 3a.

Sometimes resins produced from para-tertiary amylphenol and formaldehyde in the presence of an acid catalyst show a slight insolubility in xylene; that is, while completely soluble in hot xylene to give a clear solution they give a turbid solution in cold xylene. Such turbidity or lack of solubility disappears on heating, or on the addition of diethylethyleneglycol.

We have never noticed this characteristic property when using the commercial phenol of Example 5a which, as stated, is a mixture containing 95% para-tertiary amylphenol and 5% orthotertiary amylphenol. In fact, the addition of 5% to 8% of an ortho-substituted phenol, such as ortho-tertiary amylphenol to any difunctional phenol, such as the conventional para-substituted phenols herein mentioned, usually gives an increase in solubility when the resulting resin is high melting, which is often the case when formaldehyde and an acid catalyst are employed.

Example 6a The phenol employed (164 grams) was orthotertiary amylphenol which is a liquid. 'I'he procedure followed was the same as that used in Example 1a, and the appearance of the resin was light amber in color and transparent. It was soft to pliable in consistency and xylene-soluble.

The phenol employed (178 grams) was paratertiary hexylphenol. This is a solid at ordinary temperatures. The procedure followed was the same as that used in Example 1a preceding, and the appearance of the resin was substantially the same as that of the resin of Example 3a. The solvent-free resin is slightly opaque in appearance, reddish-amber in color, semi-hard to pliable in consistency, and xylene-soluble.

Example 8a The phenol employed was commercial paraoctylphenol. 206 grams of this phenol were employed instead of 164 grams ot an amylphenol or 150 grams of a butylphenol and 150 grams of xylene were used instead of 100. Otherwise, the procedure was the same as that used in Example 1a. The solvent-free resin obtained was reddish-amber in color, soft to pliable in consistency, and xylene-soluble.

Example 9a Grams Para-phenylphenol 170 Formaldehyde, 37% 81 HC1 (concentrated) 1.5

Monoalkyl (C10-C20, principally C12-C14) benzene monosulfonic acid sodium salt-- 0.8 Xylene 150 Diethyleneglycol diethylether 50 This phenol was solid. The phenol, xylene, diethyleneglycol diethylether, and hydrochloric acid were mixed together and heated to give complete solution at approximately C.Y The use of diethyleneglycol diethylether, or some equivalent solvent, was necessary for the reason that this particular phenol is not sufciently soluble in xylene. Having obtained a complete solution in the manner indicated, it was allowed to cool to approximately 'l5-80 C. and, thereafter, formaldehyde was added and the procedure was the same as that used in Example 1a.

The nal product contained not only xylene but also diethyleneglycol diethylether. Since this latter does not distill out readily (boiling .point 189 C.) we did not obtain a solvent-free resin sample but used the product as such for oxyethylation. -As pointed out elsewhere, the presence of a solvent is usually desirable in the oxyalkylation step. We have, however, examined a number of para phenylphenol.- formaldehyde acid-catalyzed resins which were hard, brittle resins, and melting in the neighborhood of C. or thereabouts.

When ortho-hydroxydiphenyl is substituted for para-hydroxydiphenyl one can eliminate the diethyleneglycol diethylether and use the procedure described in Example 1a, without modification. Ortho-substituted phenols yield resins which have lower melting points than do the para-substituted phenols and are usually more xylene-soluble than resins obtained from the corresponding para-substituted phenols. The matter of the lower melting point is also illustrated in the case of para-tertiary amylphenol resins in comparison with ortho-tertiary amylphenol `resins. The resin obtained from ortho derivative and formaldehyde vmelts at about 80 C. and upward, whereas the comparable para derivative resin meltsat about C. In this instance, both resins are xylene-soluble.

Example 10a I'he same procedure was employed as in Example 1a, except that para-cyclohexylphenol, 176

grams, was employed along with 150 grams of xylene. This phenol was solid. The resulting resin minus solvents was opaque in appearance, xylene dispersible, amber in color, hard and brittle, with an approximate melting point of C. It was suil'lciently curable so as to prohibit distillation.

Example 11a The same procedure was employed as in Example 1a, preceding, using 198 grams of commercial styrylphenol and 150 grams ofxylene. Styryl phenol is a white solid. -The resin was reddish ll black in color, hard and brittle, with a melting point of about 80 to 85 C.

Example 12a Grams Para-tertiary amylphenol (1.0i mole) 1 64 Formaldehyde, 37% (0.8 mole) 64.8 Glyoxal, 30% (0.1 mole) 20.0 Concentrated HC1 2 Monoalkyl (C-Cao, principally C12-C14) benzene monosulfonic acid sodium salt .75

Xylene 150 Example 13a Grams Para-tertiary amylphenol (1.0 mole) 164 Glyoxal, 30.2% (0.5 mole) 96 Concentrated HC1 v-- 2 Monoalkyl (C10-C20, principally C12-C14) benzene monosulfonic acid sodium salt Xylene 150 The same procedure was followed as in Example la. There'was a modest precipitate of an insoluble material, approximately grams, which had an insoluble sponge-like carbonaceous appearance. It was removed by filtration of the xylene solution as in Example 12a preceding. The resulting solvent-free resin was clear, reddish amber in color, soft to fluid in consistency, and Xylene-soluble.

Example 14a Grams Para-tertiary butylphenol (1.0 mole) 150 Acetaldehyde 44 Concentrated HzSOl 2 Xylene 100 'Ihe phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described under Example la. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the Xylene, 50 grams, was then mixed with the acetaldehyde; and this mixture was added slowly to the materials in the resin pot, with constant stirring, by means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example la. Approximately 30 minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about 100 to 110 C., with the reflux temperature being determined by the boiling point ofwater. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 1a. When a sample of the able in consistency.

12 resin was freed from the solvent, it was dark red, semi-hard or pliable in consistency, and Xylene-soluble.

Example 15a The same procedure was followed as in Example 14a, except that the para-tertiary butylphenol was replaced by an equal amount of parasecondary butylphenol. The appearance of the ilnal resin on a solvent-free basis was substantially identical with the preceding example, except that is was somewhat more fluid in consistency and slightly tacky.

Example 16a The same procedure was followed as in Example 14a, except that the 150 grams of paratertiary butylphenol were replaced by 164 grams of para-tertiary amylphenol. The nal solventfree resin was clear and dark red in color. It was Xylene-soluble and semi-hard or pliable in consistency.

Example 17a Example 18a The same procedure was followed as in Example 16a except that the amylphenol employed was the phenol described in Example 5a. The appearance of the resin on a solvent-free basis was substantially the same as that of Example 16a.

Example 19a The same procedure was followed as in Example 16a except that the amylphenol employed was ortho-tertiary amylphenol. The resin 0n a solvent-free basis was transparent and reddishblack; it was soft to tacky in consistency and Xylene-soluble. 4

Example 20a The same procedure was followed as in Example 14a, except that the 150 grams of paratertiary butylphenol were replaced by 206 grams of commercial para-octylphenol. The solventfree resin was dark red in color, soft to tacky in consistency, and Xylene-soluble.

Example 21a The same procedure was employed as in Example 14a,' except that the 150 grams of paratertiary butylphenol were replaced by 170 grams of para-phenylphenol. The resin produced was at least dispersible in xylene when hot, giving the appearance of solubility. When the solution cooled, obvious separation took place. For this reason grams of diethyleneglycol diethylether were added to'the finished resin mixture, when hot, so as to give a suitable solution when' cold.

A small sample was taken before adding the diethyleneglycol diethylether and the xylene evaporated in order to determine the character of the resin. The solvent-free resin was opaque and reddish-black in color. It was soft and pli- Example 22a i The same procedure was followed as in Example 14a, except that 176 grams of para-cyclohexylphenol were employed instead of the paratertiary butylphenol. The solvent-free resin was clear, dark red in appearance, soft to pliable in consistency, and Xylene-soluble.

Example 23a The same procedure was followed as in Example 14a, except that the phenol employed was commercial styrylphenol and the amount employed was 198 grams. The resin was soft-topliable, reddish-black in color, and Xylene-soluble.

The procedure employed was essentially the same as in the Example 14a where acetaldehyde was employed, but with the difference that due to the fact that the particular aldehyde was a higher boiling aldehyde it was not necessary to dilute it with xylene. For this reason all the xylene was added to the initial mixture, and the higher boiling aldehyde was added by means of the separatory funnel arrangement. Thus, the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure used as in Example 14a. The resin, after removal of the solvent by distillation, was clear, dark amber in color, had a soft, tacky appearance and was Xylene-soluble.

Example 25a Grams Para-secondary butylphenol (1.0 mole) 150 Heptaldehyde (1.0 mole) 114 Concentrated H2804 2 Xylene 100 The same procedure was employed as in Example 24a. The solvent-free resin had physical characteristics similar to those of the resin of Example 24a.

Example 26a Grams Para-tertiary butylphenol (1.0 mole) 150 Heptaldehyde (1.0 mole) 114 Concentrated H2S04 2 Xylene 100 This resin was prepared as in Example 24a preceding, with the resulting solvent-free resin being a clear, dark amber color, semi-hard or pliable, and Xylene-soluble.

The resin was prepared as in Example 24a.

The solvent-free resin was slightly opaque, dark Y amber in color, soft to fluid, and sufficiently xylene-dispersible to permit subsequent oxyalkylation.

This resin, made as in Example 24a, in solventfree form was clear. dark amber toblack in color, semi-soft to pliable and Xylene-soluble.

Example 29a v Grams Para-tertiary amylphenol (1.0 mole) 184 Benzaldehyde (1.0 mole) 106 Concentrated H2804 2 Xylene This resin, made as in Example 24a, in solventfree form was clear, dark red. hard, brittle, had a melting point of 16o-165 C., and was xylenesoluble.

Example 30a Grams Para-secondary butylphenol (1.0 mole) Benzaldehyde (1.0 mole) 1... 106 Concentrated H2504 2 Xylene 100 Thisresln, made following the procedure employed in Example 24a, in solvent-free form was clear, mahogany in color, semi-hard or pliable and Xylene-soluble.

Example 31a Grams Para-tertiary butylphenol (1.5 mole) 225 Benzaldehyde (1.5 mole) 159 Concentrated HzS04 3 Xylene 200 Example 32a Grams Para-phenylphenol (1.5 moles) 255 Benzaldehyde (1.5 moles) 159 Concentrated HzS04 3 Xylene 200 This resin was made as in Example 24a. The

`resulting solvent-free resin was clear, dark red,

hard, and brittle, with a melting point lof 200-205 C. It was somewhat heat curable, and almost completely soluble in xylene, with some insoluble material which was dispersible. It was suitable for subsequent oxyalkylation.

- Example 33a Grams Para-cyclohexylphenol (3.0 moles) 528 Benzaldehyde (3.0 moles) 318 Concentrated H2804 6 Xylene 500 This resin, formed by combining the above reactants according to the procedure employed in Example 24a, was hard, brittle, Xylene-soluble, reddish-black in color, and had a melting point of -170 C., with a tendency towards being heat curable.

Example 34a Grams Para-tertiary amylphenol (1.0 mole)v 164 Propionaldehyde, 96% (1.0 mole) 60.5 Concentrated H2804 2 Xylene 150 The above reactants were combined according to the procedure followed in Example 24a. The resulting solvent-free resin was clear, dark amber in color, soft to pliable, and Xylene-soluble.

ananas' This resin was prepared according to the procedure employedin Example 24a. The resulting solvent-free resin was clear, soft to fluid, dark amber in color, and was xylene-soluble.

Example 36a Grams Para-tertiary butylphenol (1.0 mole) 150 Propionaldehyde, 96% (1.0 mole) 60.6 Concentrated H2SO4 2 Xylene 100 This resin'was prepared according to the procedure employed `in Example 24a. The resulting solvent-free resin was clear, dark amber in color, xylene-soluble, hard and brittle, and has a melting point of 80-85 C.

Example 37a Grams Para-phenylphenol (3.0 moles) 5 10 Propionaldehyde, 96% (3.0 moles) 182 Concentrated H2804 I 6 Xylene 500 The resulting resin, prepared according to the procedure of Example 24a, when solvent-free, was opaque, hard, black, and xylene-insoluble, but sulciently dispersible in xylene for subsequent oxyalkylation. Addition of a minor proportion of ethyleneglycol diethyl-ether completely solubilized the resin in xylene, a clear solution resulting.

Example 38a Grams Para-cyclohexylphenol (3.0 moles) 528 Propionaldehyde, 96% (3.0 moles) 182 Concentrated H2SO4 6 Xylene 500 The resulting resin, prepared according to directions in Example 24a, when solvent-freewas clear, dark amber in color, xylene-soluble, hard and brittle, and had a melting point of 84-90 C.

Example 39a Grams Para-tertiary amylphenol 164 2-ethyl-3-propyl acrolein 126 Concentrated H2504 2 Xylene 100 The procedure employed was the same as for the use of heptaldehyde, as in Example 24a. The resulting solvent-free resin was dark amber to black in color, and soft to iiuid in consistency. It was xylene-soluble.

The procedure employed was the same as for the use oi heptaldehyde, as in Example 24a. The appearance of the resin was .the same as the resin of the Example 39a.

Example 41a v Grams Commercial para-octylphenol 206 2-ethyl-3-propyl acrolein 126 Concentrated H2SO4 2 Xylene 100 'I'he procedure employed was the same as for the use of heptaldehyde, as in Example 24a.

The appearance of the resin was the same as. the resin of Example 39a.

Example 42a y j Grams Para-tertiary amylphenol 164` Furiural 96 Potassium carbonate 8 The furiural was shakenA with dry sodium carbonate prior to use, to eliminate any acids, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago,

Illinois. The above reactants were heated under the reilux condenser for two hours in the same resin pot arrangement described in 'Example la. The separatory funnel device was not employed. No xylene or other solvent was added. The amount of material vaporized and condensed was comparatively small except for the water of reaction. At the end of this heating or refluxperiod, the trap was set to remove the water. The maximum temperature during and after removal of water was approximately 202 C. The material in the trap represented' 16 cc. water and 1.5 cc. Iurfural. The resin was a bright black, hard resin, xylene-soluble, and had a melting point of 130 to 135 C., with some tendency towards being slowly curable. We have also successfully followed this same procedure using 3.2 grams of potassium carbonate instead of 8.0 grams.

Example 43a Grams Para-tertiary amylphenol 164 Furfural (carbonate treated) 'l0 Potassium carbonate 3.2

The procedure employed was the same as that of Example 42a. The amount of water'distilled was 10 cc. and the amount of furfural, 3 cc. 'I'he resin was a bright black, xylene-soluble resin, semi-pliable to hard.

Example 44a Grams Para-tertiary amylphenol 492 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (C10-C20, principally C12-Cid) benzene monosulfonic acid sodium salt-- 2.0 Xylene 200 The above reactants were combined in a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reilux for 2 hours at 100 to 110 C. The resinous mixture was thenpermitted'to cool suillciently to permit* the addition of 15 ml. of glacial acetic acid in cc. H2O. On standing, a separation was eected, and the aqueous lower layer drawn oil. The upper resinous solution was then washed with 300 ml. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed from the resinous solution by distilling under vacuum to 150 C. The

resulting resin was clear, light amber in color, and semi-fluid or tacky in consistency.

Example 45a Grams Para-secondary-butylphenol 450 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8 MonOalkyl (C-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2 Xylene 200 'Ihe same procedure was followed as in Example 44a. The resulting solvent-free resin was clear, light amber in color, and semi-fluid or tacky in consistency.

Example 46a Grams Para-phenylphenol 510 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (Cio-C20, principally C12-C14) benzene moosulfonic acid sodium salt Xylene 500 The same procedure was employed as in Example 44a, except that the reaction product contained a considerable amount of a white crystalline solid which was alcohol-soluble and xyleneinsoluble, necessitating the use of some isopropyl alcohol in eecting a separation. The resulting solvent-free resin had a grayish-white crystalline structure, and was hard, brittle, non-Xylenesoluble but soluble in a xylene-diethyleneglycol diethylether mixture. This crystalline structure in phenylphenol resins has been noted in the literature.

Example 47a Grams Para-cyclohexylphenol 528 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2.0 Xylene 300 This resin was made and worked up in the same manner as in Example 46a. The resin, after distillation and standing overnight, developed the same type of crystalline structure noted in the resin of the Example 46a. However, on cooling immediately after distillation, the resulting product was clear, light amber in color,

and fairly soft in consistency.

Example 48a Grams Para-tertiary'butylphenol 450 Formaldehyde, 30% 652 NaOH in 30 cc. H2O 6.8 Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonie a'cid sodium salt 2 Xylene L 300 The same procedure was followed as in Example 44a. The resulting resin was deep red in color, clear, and soft or semi-iluid in consistency.

Example 49a This resin was prepared as in Example 44a except that the para-tertiary amylphenol-formaldehyde ratio was l to 1.1 moles. The resulting solvent-free resin was dark red in color, clear, and semi-hard or pliable in consistency.

Example 50a The resin was prepared as in Example 48a except that the para-tetiary butylphenol-formaldehyde ratio was 1 to 1.1 moles. The resulting solvent-free resin was dark red in color, clear,

soluble, infusible occulent precipitate was noted dispersed throughout the resinous solution. This was filtered out before distillation. The resin, after vacuum distillation to C. to remove the solvent, was dark red in color, clear, hard and brittle, with a melting point of 113-117" C.

Example 52a Resin of Example 44a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was a hard, brittle resin, xylenesoluble, and having a melting point of 145-150" C.

Example 53a Resin of Example 45a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. -The resulting product was hard, brittle, black in color, Xylene-insoluble, and intusible up to 220 C. However, if the vacuum distillati was taken to only 175 or 180 C., at 25 mm. Hg the resulting product was Xylene-soluble and ad a melting point of approximately 170 C.

Example 54a Resin of Example 46a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was opaque or crystalline, xylene-dispersible, and soluble in a mixed solvent of 75% xylene and 25% diethyleneglycol diethylether, with a melting point oi' 10o-105 C.

Example 55a Resin of Example 47a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was opaque or crystalline, dark brown in color, xylene-so1uble, and semi-hard or pliable in consistency.

i Example 56a Resin of Example 48a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was hard, brittle, partially Xylene-insoluble, but soluble in a mixed solvent of 75% Xylene and 25% diethyleneglycol diethylether with an approximate melting point of 1GO-165 C. It was also heat curable.

Example 57a Resin of Example 49a was subjected to-vac.

uum distillation to 225 C., at 25 mm. Hg. The resulting product was dark amber to black in color, Xylene-soluble, hard and brittle, with a melting point of 145-150 C.

Example 58a Resin of Example 50a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting resin was black in color, hard and brittle, Xylene-dispersible, and soluble in a mixed solvent of 75% xylene and 25% diethyleneglycol diethylether, with a melting point of -170 C. It was also heat curable.

Example 59a Resin of Example 51a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The

Monoalkyl (C-Cn, principally C12-Cu) benzene monosulfonic acid sodium salt- 1.5

The above reactants were reiluxed with stirring for 2 hours. 200 grams of xylene were then added and the whole cooled to 90-100 C., and the NaOH neutralized with 10 ccnglacial acetic acid in 100 cc. H2O. The mass was allowed to stand, eilecting a separation. The lower aqueous layer was withdrawn and the upper resinous solution was washed withwater. After drawing oil' the wash water, the xylene solution was subjected to vacuum distillation, heating to 150 C. The resulting solvent-free resin was xylene-soluble, soft or tacky in consistency, and pale yellow or light amber in color.

On heating further, without vacuum distillation, the following physical changes were noted:

The above distillation was without the use of vacuum. It illustrates that heating alone, or heating with vacuum, changes a low-stage resin into a medium or high-stage resin.

Example 61a This resin was obtained by the vacuum distillation of resin of Example 3a. Vacuum distillation was conducted up to 250 C. at 25 mm. Hg. The resulting resin was hard, brittle, amber colored, y and had a slightly higher melting point than the resin prior to vacuum distillation, to wit, 14o-145 C. It was xylene-soluble. The: molecular weight, determined cryoscopically using benzene, was approximately 1400.

Example 62a This resin was obtained by the vacuum distillation of resin of Example 8a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was xylene-soluble, hard, brittle, reddish black in color, with a melting point of 140-145" C. Note that this resin, prior to vacuum distillation, was soft to pliable in consistency.

Example 63a This resin was obtained by the vacuum distillation of resin of Example 10a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was xylene-dispersible, soluble in a mixture of xylene and diethyleneglycol diethylether, dark brown in color, and hard and brittle in nature. It had a melting point of 18o-185 C.

This was moderately higher than the resin prior to vacuum distillation.

Example 64a This resin was obtained by the vacuum distillation of resin of Example 9a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was semi-hard but still contained some diethyleneglycol diethylether. Unquestionably, if completely separated from this solvent it would have been a hard solid resin. Such residual solvent was not eliminated lest there be danger of pyrolysis.

Example a This resin was obtained by the vacuum distillation of resin of Example 16a. Vacuum distillation was conductedup to 225 C. at 25 mm. Hg. The resulting resin had the same physical characteristics as the undistilled resin except that it was slightly more viscous.

Example 66a This resin was obtained by the vacuum distillation of resin of Example 15a. Vacuum distillation was conducted up to 225 C. at 25 mm, Hg. The resulting resin was semi-hard to pliable.

Example 67a This resin was obtained by the vacuum distillation of resin of Example 20a. Vacuum distillation was conducted up to 225 C. at 25 mm Hg. The resulting resin was hard to pliable.

In the immediately preceding examples describing the production of resins by the vacuum distillation of resins of earlier examples, the vacuum used was approximately 25 mm. and the temperature was brought up to 225 C. Generally speaking, this is about the maximum temperature which is lusable, and if the products obtained on distilling to this temperature, even if xylene-soluble, give insoluble or rubbery products on oxyethylation, the temperature used should be lower. We have found that using a temperature of 190 C. at 25 mm. gives very satisfactory compounds which have little tendency' to form rubbery derivatives during oxyethylation.

Monoalkyl Cin-Cm, principally C12-C14) benzene monosulfonic acid sodium salt-- .8 Xylene 200 No catalyst was added in this example. The reactants were placed in an autoclave and stirred while heating to a temperature of approximately 160 C. The total period of reaction was 5% hrs. During the early part of this period the temperature was 156 C. with a gauge pressure of 110 pounds. During the last part of the period, probably due to the absorption of formaldehyde, the pressure droped to pounds gauge pressure while the temperature held at about C. After this 5% hour reaction period the autoclave was allowed to cool. The liquids were withdrawn and the xylene solution of the resin was decanted away from the small aqueous layer. The xylene solution, containing a bit of the aqueous layer carried over mechanically, was subjected to vacuum distillation up to 150 C. at 25 mm. Hg. i

The resulting resin was fairly hard and brittle',

xylene-soluble, dark, amber in color, with a melt- 21 higher presume so as to speed up the reaction and also in order to obtain resins o1' higher molecular weight. We have employed the same procedure with moderately higher temperatures and detinitely higher pressures.

Example 69a Grams Menthylphenol, technically pure (1.0 mole) 232 Formaldehyde, 37% (1.0 mole) 81 Concentrated HCl 2 Monoalkyl (Cw-Cm, principally C12-C14) benzene monosulfonic acid sodium salt 2 Xylene 200 The same procedure was followed as in Example la. The solvent solution so obtained was used as such in subsequent oxyalkylation steps. We have also removed the solvent by conventional means, such as evaporation, distillation or vacuum distillation. The resin obtained in the operation above described was clear, reddish amber in color, hard, brittle and had a melting point of about 115 to 120 C.

Example 70a Grams Nonylphenol (para) (3.0 moles) 660 Formaldehyde, 37% (3.0 moles) 243 Concentrated HC1 9 Monoalkyl (C-Cm, principally C12-C14) benzene monosulfonic acid sodium salt-- 2.5 Xylene 300 I'he procedure followed was the same as that used in Example 1a; The phenol employed was a heavy, sirupy liquid, largely or almost entirely para with possibly a small percentage of ortho present. The solvent-free resin was clear, reddish amber in color and semi-soft or pliable in consistency.

Example 71a Grams Octadecylphenol (1.0 mole) 346 Formaldehyde, 37% (1.0 mole) 81 Concentrated HCl 3.2

Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 1.6 Xylene 200 The procedure followed was the same as that used in Example 1a preceding. The phenol employed was a liquid. It was largely or entirely the para isomer with possibly a small amount of ortho present. 'Ihe resulting solvent-free resin was soft to pliable in consistency, clear and reddish amber in color.

Example 72a Grams Crude para-cumylphenol (1.27 moles) 268 Formaldehyde, 37% (2.0 moles) 162 Concentrated HC1 2.5

Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 1 Xylene 250 22 hard but not particularly brittle. .It had a melting Point 0f 80 t0 85 C.

Example 73a Grams Para-decylphenol (1.0 mole) 234 Formaldehyde, 37% (1.0 mole) 81 HC1 (concentrated) 2 Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt-- 1.2 Xylene 200 The procedure followed was the same as that used in Example 1a preceding. The phenol was a straw colored liquid, having a little phenolic odor. 'Ihe solvent-free resin obtained was reddish amber in color and semi-soft or pliable in consistency.

Example 74a Grams Para-dodecylphenol (1.0 mole) 262 Formaldehyde, 37% (1.0 mole) 81 HC1 (concentrated) 3.5

Monoalkyl (Cio-C20, principally C12-C14) v benzene monosulfonic acid sodium salt 2.5 Xylene 250 'I'he procedure followed was the same as that used in Example 1a. The phenol was a straw colored liquid, having a little phenolic odor. The solvent-free resin obtained was deep red in color and semi-soft or pliable in consistency.

Example 75a Grams Nonylphenol (1.0 mole) 220 Formaldehyde, 37% (0.865 mole) 'l0 Glyoxal, 30% (0.065 mole) 12.5 Concentrated HC1 2 Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 0.8 Xylene Example 76a Y Grams Menthylphenol, technically pure (1.0 mole)- 232 Acetaldehyde (1.0 mole) 44 Concentrated H2SO4 2 Xylene 100 The phenol, acid catalyst, and 50 grams of the Xylene were combined in the resin pot previously described under Example 1a. The initial mixture did not include the aldehyde.v 'I'he mixture vwas heated with stirring to approximately C. and permitted to reflux.

The remainder of the xylene, 50 grams, was then mixed with the acetaidehyde; and this mixture was added slowly to the materials in the resin pot, with constant stirring, by means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example la. Approximately 30 minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted at the first addition of the aldehyde. 'I'he temperature slowly dropped, as water of reaction formed. to about 100 to 110 C., with the reux temperaaseaaos and had a melting point of about 50 to 55 C.

' Example 77a Grams Nonyiphenol, para (0.773 mole) 170 Acetaldehyde (.773 mole) 34 Concentrated H2804 3 Xylene 75 The same procedure was followed as in Example 76a, except that nonylphenol was used instead of menthylphenol. The solvent-free resin was reddish amber in color and soit to pliable in consistency.

Example 78a Grams Octadecylphenol (0.5 mole) 173 Acetaldehyde (0.5 mole) 22 Concentrated H2804 1 Xylene 75 The same procedure was followed as in Example 76a, except that octadecylphenol was used instead of menthyiphenol. The solvent-free resin was soit to semi-brittle in consistency and dark red in color.

Example 79a Grams Menthylphenol (3.0 moles) 696 Heptaldehyde (3.0 moles) i34:3 Concentrated H2804 6 Xylene 500 The procedure employed was essentially the same as in Example 76a where acetaldehyde was employed, but with the dilierence that due to the fact that heptaldehyde is a higher boiling aldehyde, it was not necessary to dilute it with xylene. For this reason all the xylene was added to the initial mixture, and the heptaldehyde was added by means of the separatory funnel arrangement. Thus, the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure used in Example 76a. The resin, after removal of the solvent by distillation, was clear, dark red in color, had a soit, tacky appearance and was xylene-soluble.

Xylene The same procedme was followed as in Example 79a preceding. The solvent-free resin was dark amber in color and semi-fluid or tacky The procedure followed was the same as in Example 79a. The solvent-free resin was semihard to pliable and reddish amber in color.

' Example 82a Grams Nonylphenol (1.5 moles) 330 Benzaldehyde (1.5 moles) 159 Concentrated H2804 3 xylene N 200 The procedure followed was the same as in Example 79a. The solvent-free resin was clear. semi-soft to pliable and dark amber in color.

Example 83a l Grams Menthylphenol (1.0 mole) 232 Propionaldehyde, 96% (1.0 mole) 60.5 Concentrated H2804 2 Xylene 150 Thesame procedure was followed as in Example 79a. The solvent-free resin was dark amber in color, semi-hard or pliable in consistency, with a tendency towards tacklness.

Example 84a v Grams Nonyiphenol (1.0 mole) 220' Propionaldehyde, 96% (1.0 mole) 60.5 Concentrated H2804 v2 150 The same procedure was followed as in Example 79a. The solvent-free resin was dark amber in color and semi-fluid or tacky in consistency. f

The same procedure was followed as in Example 79a. The solvent-free resin was black in color and soft to uid in consistency. v

Example 86a vGrams r. Menthylphenol (1.0 mole) 232 2ethyl3propyl acrolein (1.0 mole) 126 Concentrated H2804 2.5 xylene 150 The same procedure was followed as in Example 79a. The solvent-free resin was black in color and soft to iiuid in consistency.

x Example 87a Grams Menthylphenol (2.0 moles) 464 Formaldehyde, 37% (5.0 moles) 405 NaOH in 30 c. c. H2O 6.8 Monoalkyl (Cm-C22, principally C12-C14) benzene monosulfonic acid sodium salt Xylene 300 The above reactants were combinedin a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reflux for 2 hours at to 110. The resinous mixture was then permitted to cool suiiiciently to permit the addition of 15 mi. of glacial acetic acid in 150 c. c. H2O. 0n standing, a separation was effected and the aqueous lower layer drawn oii'. The upper resinous solution was then washed with 300 mi. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed from the rinous solution by distilling under vacuum to C. The solventfree resin was light amber in color, non-brittle, and semipliable to hard.

Example 88a Nonylphenol (3.0 moles) grams-- 660 Formaldehyde, 30% (6.6 moles) do 652 NaOH in 30 c. c. H2O do 6.8 MOnOalkyl (C10-C20, principally C12-C14) benzene monosulfonic acid sodium salt grams-- 2 Xylene -d 300 Glacial acetic acid ml-- 15 The procedure used was the same as that of Example 87a. The solvent-free resin was clear, dark amber in color and soft to fluid in consistency.

Example 89a' Nonylphenol (3.0 moles) grams 660 Formaldehyde, 30% (3.3 moles) do 330v NaOHin 30 c.c.H2O do 6.8 Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt graxns-- 2 Xylene do 100 Glacial acetic acid ml 15 The same procedure was followed as in Example 87a. 'I'he solvent-free resin was clear, dark red in color and semi-fluid or tacky in consistency.

Example 90a Grams Nonyllphenol (1.0 mole) 220 Furfural (Na2CO3 treated) (1.0 mole) 96 Potassium carbonate 12 Xylene 200 'I'he furfural was shaken with dry sodium carbonate prior to use to eliminate any acids, etc. The procedureemployed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The materials, except the xylene, were heated under the reux condenser for two hours in the same resin pot arrangement described in Example la. At the end of this heating or reux period the trap was set to remove the water, and the Xylene added after most of the water had distilled.

The maximum temperature during and after removal of water was approximately 205 C. The resin was a reddish black, clear resin, Xylenesoluble, and semi-soft to pliable in consistency.

Example 91a Grams Menthylphenol (1.0 mole) 232 Furfural (Na2CO3 treated) (1.0 mole) 96 Potassium carbonate 12 Xylene 200 The procedure followed was identical with that in Example 90a. The solvent-free resin was reddish black in color, hard, brittle, with a melting point of 158 to 163 C., and showed a deiinlte tendency towards being heat curable.

Example 92a A duplication of the resin described under the heading of Example 88a was prepared and subjected to distillation. Distillation without vacuum was rst employed to eliminate the xylene. After the elimination of Xylene the resin was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting resin was .black in color, semi-fluid but of distinctly greater viscosity or hardness than v the undistilled resin, and Xylene-soluble.

was still perfectly Example 93a A duplicate sample of the resin described under the heading Example 89a was prepared and subjected to vacuum distillation, in the same manner as described in Example92a, preceding. The resin obtained by the vacuum distillation was reddish-black in color, had a melting pointiof 100 to 105 C., and was Xylene-soluble.

Example 94a A duplicate of the resin described in Example 69a was prepared and subjected to vacuum distillation in the same manner as described in Example 92a. The resulting resin was a hard, brittle, amber colored resin, Xylene-soluble and had a melting point of 145 to 150 C.

. Example 95a i A duplicate of the resin described in Example 70a `was prepared and subjected 'to distillation. including vacuum distillation, in the same manner as described in Example 92a. The resulting resin was a clear, hard, brittle, Xylene-soluble resin,

amber colored, and had a melting point of to C.

Example 96a A duplicate of the resin described in Example 87a was prepared and subjected to distillation, including vacuum distillation, inthe same manner as described in Example 92a. I'he resulting product was hard and brittle, with a melting lpoint of to 140 C. Otherwise the physical characteristics were approximately the same as in the non-distilled product.

Example 97a y Grams Nonylphenol (3l moles) y6,320 Formaldehyde, 37% (42 moles) `3,430 NaOH (in 200 c. c. H2O) 93 Xylene 2,040

The above reactants were combined in a 5-gallon autoclave and heated ywith stirring inthe following manner: l

,Pounds 'fer stopped at this lpoint,l suffrwas" appliedf'to lower the temperature to approximately "80V`C., orl cool enough to `permit opening the autoclave'and add- The reaction was cient cooling water glacial acetic acid to neutral- Monoalkyl (Cio-Cao, principally C12-C14) benzene monosulfonic acid sodium salt-- 15 NaOH (in 200 c. c. H2O) 67 xylene 4,000

The above reactants were combined in a 5- gallon autoclave and heated with stirring, under pressure. The reactants were heated for 1% hours after temperature had reached 110 C. The maximum temperature was 190 C. and the maximum pressure was f 245 pounds per square inch.

After cooling, more than suillcient (148 grams) glacial acetic acid was added to neutralize the alkaline catalyst. The resin mixture was diluted, washed and distilled in a manner similar to that in the Example 97a.. The resulting solvent-free resin, after vacuum (25 mm.) distillation to 150 C., was semi-hard to pliable, amber colored, and xylene-soluble. If the vacuum distillation is further carried to 200 C., the resulting product is a hard, brittle resin with a melting point of 90 to 95 C. It is amber in color and xylene-soluble. 5

Example 99a Grams Nonylphenol (34 moles) '1,470 Formaldehyde, 37% (38 moles) 3,114 Xylene 2,020 Catalyst None The above reactants were combined in a 5-gallon autoclave. They were heated with stirring under pressure for a total heating time (time starting when temperature reached 100 C.) of 5 hours with a maximum temperature of 200 C., and maximum gauge pressure of 235 pounds per square inch.

After removing the resin mixture from the autoclave, it was diluted further with approximately 7000 grams of xylene. This was done to thin the resin sufficiently to permit a ready seperation of the water and unreacted formaldehyde. After twice washing the xylene resin solution with water to assure the removal of any unreacted formaldehyde, the solution was subjected to vacuum distillation (25 mm.) to 145 C., to remove the xylene.

The resulting resin was clear, xylene soluble, amber colored and semi-hard or pliable in consistency.

Example 100a Grams Para-ethylphenol, technically pure (2.0

moles) 244 Formaldehyde, 37% (2.06 moles) 167 Concentrated HC1 3.8

Monoalkyl (Cio-Cao, principally C12-C14) benzene monosulfonic acid sodium salt 1.5 Xylene 200 heat. This period of gentle reux was continued 75 for approximately one-half hour. At the end of this time there was obtained a viscous, creamy mass. The 200 grams of xylene previously indicated were added to the reaction mass during this creamy stage so as to thin it sufllciently to permit eilicient agitation. The solvent-diluted mass was refluxed for one hour longer at approximately 105 C. before attempting to remove the water by the usual trap arrangement. At this point, that is after 11/2 hours reiluxing, the trap arrangement was changed from the reflux position to the normal water entrapment position. The water of solution and the water of reaction were permitted to distill out and collect in the trap. As the water distilled out the temperature gradually increased to approximately 150 C., which required somewhat less than three hours. The solvent-free resin was amber in color, xylene soluble and had a comparatively high melting point, to wit, 200 to 210 C. The final product contained approximately xylene and 60% resin.

Example 101a Grams Para-ethylphenol, technically pure (2.0

moles) 244 Formaldehyde, 3I%% (2.05 moles) 162 Concentrated HC1 2.5 Monoalkyl (Cio-Cao, principally Cin-C14) benzene monosulfonic acid sodium salt 1.0

Xylene water of reaction were HC1 (concentrated) It will be noted that the reactants in this example are substantially the same as in the preceding example. The amount of xylene used, however, is somewhat less. In the instant procedure the xylene was added at the beginning of the reaction. More specically, the procedure is as follows. The equipment used was the same.

In this instance the phenol, Iformaldehyde, acid catalyst and solvent were combined in the resin pot above described. Heat was applied with gentle stirring and the temperature was raised to -85 C. at which point an exothermic reaction took place. This reaction raised the temperature to approximately 110 C. The reaction mixture was then permitted to reflux at 100-105 C., for between one and 11/2 hours. The reilux trap .arrangement was then changed from the reflux position to the normal water entrapment position. The water of solution and the permitted to distill out and collect in the trap. As the water distilled out the temperature gradually increased to approximately C., which required between 11/2, to 2 hours. At this point the water recovered in the trap, after making allowance for a small amount of water held up in the solvent, corresponded to the expected quantity.

Example 102e Example 103a Grams Para-isopropylphenol,1 technically pure (1.0

mole) Formaldehyde, 37% (1.0 mole) 81 Monoalkyl (Cio-Cao, principally C12-C14) benzene monosulfonic acid sodium salt- .8

, Grams Xylene 100 Diethyl Carbitol (Diethyl Carbitol is a trade name for the diethyl ether of diethylene glycol) 50 lnl'n-isopropylpllenol is n white solid.

was made to obtain any solvent-free resin in' order to determine its appearance or melting point.

Example 104a The phenol employed was ortho-isopropylphenol. This was a viscous liquid, having a pale amber color. Otherwise the procedure followed was the same as that in the preceding example. The resin seemed to be distinctly more Xylenesoluble than the corresponding resin obtained from the para derivative. The Diethyl Carbito). was added purely by way of precaution.

Example 1.05a

Grams Thymol (1 mole) 151 Formaldehyde, 37% (1 mole) 81 HC1 (concentrated) Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 0.8

Xylene 200 T-he same procedure was followed as in Example 101a. The solventfree resin was a hard, brittle amber colored product, with a melting point of 148 to 153 C. The resin showed some tendency towards being heat curable. The

thymol employed was of pharmaceutical quality.

Example 106a Grams Para-ethylphenol (2.0 moles) 244 Acetaldehyde (2.0 moles) 88 Concentrated H2SO4 2.5 Xylene 150 The phenol, acid catalyst, and 50 grams of Xylene were combined in the resin pot previously described. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the Xylene, 100 grams, was then mixed with the acetaldehyde; this mixture wasv added slowly to the materials in the resin pot, with constant stirring, by means of the separatory funnel arrangement. Approximately 30 minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted Iat the rst addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about 100 to 110 C., with the reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to 1%/2 hours before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 100a. The solvent-free resin was reddish black in color and soft to pliable in conlample 106a. The resin 30 sistency. The resin solution as tained just a trifle over 30 xylene.

Ezrample 107a .obtained con- Grams Para-ethylphenol v(2.0 moles) f 244 Propionaldehyde,`96% (2.0 moles) 12.1 Concentrated H2804-.. 2.5 Xylene 150 f The procedure followed was the same as that described under Example 106a. The solventfreevresin was dark amber in color, and soft to pliable in consistency. The resin solution contained a. little in excess of 30% xylene.

Example 108a Grams Para-ethylphenol (2.0 moles) 244 Benzaldehyde (2.0 moles) 212 Concentrated HzSO4 2.5 Xylene 150 The procedure followed was the same as that described in Example 106a. The solvent-free resin was clear, reddish amber in color, and semihard or pliable in consistency. The solution contained a little over 25% xylene.

Example 109a A Grams Para-isopropylphenol (1.0 mole) 136 Benzaldehyde (1.0 mole) 106 Concentrated H2SO4 1.8 Xylene The same procedure was followed as in Example 106a. The resin obtained was opaque or dark amber to black in color, and soft to uid in consistency. This solution contained somewhat less than 30% xylene.

Example 110a Grams Para-ethylphenol (2.0 moles) 244 Butyraldehyde (1.05 moles) 75.6 Concentrated H2S04 4.0 Xylene 100 The same procedure was followed as in Example 106a. The resin obtained was dark red in color and soft to fluid in appearance. The solutionA contained approximately 25% Xylene.v

Example 11`1a` "'Grams Para-ethylphenol (2.0 moles) 244 Heptaldehyde (1.05 moles 119.5 Concentrated I-I2S04 4 Xylene 100 The same procedure was followed a`s in Exobtained was dark red in color, fluid in consistency, and the solution contained 221/2% Xylene. y

, Example v112a Grams A 244 Furfural (treated with NazCOs) (2.0 moles) 192 Potassium carbonate 12 Xylene 250 The furfural was shaken with dry sodium carbonate prior to use to eliminate any acids, etc. The procedure employed. was `substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The reactants were heated under the reflux condenser for two hours in the same resin pot arrangement. The separatory funnel device was not employed. n No Xylene or other solvent was Para-ethylphenol (2.0 moles) i resinication was complete, as a matter of convenience instead of pouring the hot resin and subsequently dissolving it in xylene, the amount of xylene indicated was added simply for purposes of dilution. The product contains about 38% xylene.

Example 113a Grams Para-ethylphenol (4.0 moles) 488 Formaldehyde, 37% (4.4 moles) 356 NaOH in 30 c. c. H2O 6.8 Xylene 350 The above reactants were combined in a resin pot similar to that previously described. equipped with stirrer and reux condenser. The reactants were heated with stirring under reflux for 2 hours at 100 C. to 110 C. The resinous mixture was then permitted to cool sufficiently to permit the addition of ml. of glacial acetic acid in 150 c. c. H2O. On standing, a separation was e'ected, and the aqueous lower layer drawn oil. The upper resinous solution was then washed with 300 ml. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed fromvthe resinous solution by distilling under vacuum to 150 C. The product was semi-hard to pliable and light amber in color. The solution as prepared contained approximately 36% xylene.

Example 11441 Grams Para-isopropylphenol (4.0 moles) 544 Formaldehyde, 37% (4.4 moles) 356 NaOH in 30 c. c. H2O 6.8 Xylene 350 A resin was made which was the duplicate of that of Eixample 1l1a. This resin was then heated under vacuum so as to eliminate the xylene and alsocause further polymerization.

Example 116a l The same procedure was followed'as in Example 115a but instead of using a resin prepared from para-ethylphenol as described in there was employed instead a resin 244 grams of Example lila,

made in the same manner from para-isopropylphenol, in which 272 grams of the isopropylphenol replaced the 244 grams of para-ethylphenol. Otherwise the procedure was identical with that described in Example 111a. The vacuum distillation of-the resin so obtained was exactly identical with that described in Example 1l5a.

No catalyst was used. The reactants were placed in an autoclave and stirred while heating to a temperature of approximately 165 C. The total period of reaction was 9% hours. During the early part of this period the temperature was 167 C. with a gauge pressure of 150 pounds. During the last part of the period. the pressure was 140 pounds gauge pressure while the temperature held at about 150 C. After this 9 V2 hour reaction period the autoclave was allowed to cool. The liquids were withdrawn and the xylene solution of the resin was decanted away from the small aqueous layer. To the xylene solution were added 1,000 grams of xylene, and the solution was washed several times to remove excess formaldehyde. The solvent and any water were removed by vacuum distillation to 150 C. at 20 mm.. giving a reddish-black, semi-viscous or fluid, xylenesoluble resin. If desired, one may use considerable higher pressures so as to speed up the reaction and also in order to obtain resins of higher molecular weight. We have employed the same procedure with moderately higher temperatures and definitely higher pressures.

Monoalkyl (Cm-zo, principally C12-C14) benzene monosulfonic acid sodium salt.- 0.8 Xylene The phenol used was paracresol of commerce. The procedure followed was that described in Example la. The resin was dark and brittle, and melted at 114-120 C.

`Example 119a The same procedure was followed as in Example 118a except that commercial orthocresol was used instead of commercial paracresol. The resulting resin was a dark brown resin. v

Example 120a The same pn edure was followed as in Example 118a except that 122 grams of xylenol of the following structure were employed instead of the 'v cresol:

Example 12m Grams Paracresol (3.0 moles) 324 Acetaldehyde (3.0 moles) 132 Concentrated H2804 8 Xylene 100 The phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately C. and permitted in Il reilux.

- reflux temperature being determined by the boi1 ing point of water. After all the aldehyde had been added. the reactants were permitted to rep flux for between an hour to an hour and a half before removing the water by means of the trap arrangement.l After the water was removed the remainder of the procedure was essentially the same as in Example 118a. The resin obtained was a semi-hard pliable material of reddish amber color. e

Example 122a Grams Paracresol (2.0 moles) 216 Benzaldehyde (2.0 moles) 212 Concentrated H2804 5 Xylene 100 The procedure employed was essentially the same as in Example 121a where acetaldehyde was employed, but with the difference that due to the fact that the particular aldehyde was a higher boiling aldehyde it was not necessary to dilute it with the Xylene. For this reason all the xylene was added to the initial mixture, and the higher boiling aldehyde was added by means of the separatory funnel arrangement. Thus, the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure used as in Example 121a. The resin was reddish in color and brittle in consistency.

Example 123a Grams Orthocresol (2.0 moles) 216 Butyraldehyde (2.0 moles) 144 Concentrated HzSOi 4 Xylene 100 The procedure followed was identically the same as that in Example 122a. The solvent-free resin obtained was soit to tacky in consistency.

Example 124a The procedure followed was the same as that used in Example 122a. The solvent-free Vresin obtained was dark red in color and soft to nuid in consistency.

Example 125a G 1,3,4 xylenol (sometimes called 1.2.4, xylenol) (2.0 moles) 244 Heptaldehyde (2.0 moles) 228 Concentrated H2804 4 Xylene 100 The procedure followed was the same as that used in Example 122a. The solvent-free resin obtained was soft to fluid in consistency and reddish black in color.

7g caprate. The resin Example 12Go Grim# Paracresol (1.0 mole) 108 Furfural (1.0 mole) 96 Potassium carbonate 8 The furfural was shaken with dry sodium carbonate prior to use, to eliminate any acids, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The above reactants were heated under the reiiux condenser for two hours in the same resin pot arrangement described in Example 118a. The separatory funnel device was not employed. No xylene or other solvent was added. The amount of material vaporized and condensed was comparatively small except for the water of reaction. At the end of this heating or reflux period, the trap was set to remove the water. The maximum temperature during and after removal of water was approximately 202 C. The material in the trap represented 16 cc. water and 1.5 cc. furi'uraL The resin was dark and summy. Example 127a Grams Paracresol (0.9258 mole) Formalin (1.15 moles) 95.81 Abietic acid (0.06 mole) 20 Ammonium hydroxide (30%) 3 The reactants were placed in a three-necked 500 cc. flask and stirred until the abietic acid had dissolved. stirring was continued and the contents heated to about 97.5 and reiluxed at this temperature for 45 minutes. At this time a trap arrangement was added to the apparatus so as to remove the waterin the conventional manner. At the time the removal of water started there was no apparent separation of the mixture. Approximately 88 grams of water were removed and the product heated at approximately C. for

15 minutes after no more water came over. The final product wasl a dark brittle resin.

Example 128a i. Grams Eicosanyl phenol (90% purity as described) (1.0 mole) 416 Formaldehyde (37%) (1.1 moles) 90 Concentrated HC1 l Monoalkyl (Cio-Cao, principally C12-C14) benzene monosulfonic acid sodium salt... 1.5 Xylene 150 The eicosanyl phenol was a dark amber colored viscous liquid obtained by the alkylation of phenol with the tertiary carbinol obtained by the Grignard reaction of ethyl caprate and amyl bromide in molar proportions of 1:2. This material contained at least 90% substituted phenol considered to be `primarily para-substituted with some orthoand perhaps an insigniiicant amount of meta-substituted phenol. The procedure iol-` lowed was that of Example 1a. vThe resulting resin was amber colored, hard, and with a somewhat tacky feel, possibly the result of the 10% impurities in the phenol used.

' Example 129a The procedure was the same as that of Example 128a except that the 416 grams of eicosanyl phenol were replaced by 447 grams of docosanyl phenol, prepared in the same way but with the use oi' ethyl laurate instead of ethyl obtained was similar in apthe appearance was casca pearance to that of Example 128e but was somewhat softer.

Example 130a The procedure followed was the same as that of Example 128a except the eicosanyl phenol was replaced by 478 grams of tetracosanyl phenol, prepared in the same manner but with the use of ethyl myristate. The resin obtained was similar in appearance to that of Example 128a but was considerably softer. l

Phenols with hydrocarbon substituents containing 20 to 24 carbon atoms have also been prepared in other ways, for example, by the monochlorination of waxes from Pennsylvania crudes having molecular Weights indicating the presence of 20 to 24 carbon atoms in the molecule. A phenol prepared in this way, using zinc chloride as the alkylation catalyst, converted to a resin as in Example 128a by using 447 grams of the phenol to allow for the presence of impurities, gave a dark, tacky to semi-hard resin. The cut was selected to have an average molecular weight of 22 carbon atoms, to give a mixture of difunctional phenols with 20 to 24 carbon atom substituents, although the presence of lighter or heavier materials in the selected fraction, which presumably carried over in'to the phenol, is not improbable, because a product having an average molecular weight of, say, 22 carbon atoms, is equivalent to either a Cao-Cu fraction or a Cn- Czs fraction, etc.

Monoalkyl (Cio-Cso, principally Cia-C14) benzene monosulfonic acid sodium salt-- 1.5 Xylene 200 The procedure followed was the same as that of Example 1a. The solvent-free resin was hard, brittle, amber. and melted at 135-140". C.

Example 1320,`

The resin was made in the same manner as outlined in Example 131e. except that 1,3,4 xylenol (1,2,4 xylenol counting the methyl position as No. 1 position) was substituted in molecular proportion for the orthocresol. Thus, instead of using 108 grams of orthocresol there was used 122 grams of xylenol. In all other respects the procedure was identical. The resulting resin, minus solvent, was somewhat harder than that obtained employing orthocresol. It had a melting point of about 160 to 165 C., but otherwise the same as that of the resin derived from cresol.

Example 1336 Example 134a AThe same procedure was followed as in Example 131a, except that the orthocresol was replaced the para-ethylphenol phenol.

by xylenol and the ethylphenol by Dar-tertiaryamylphenol. Thus, instead of using 108 grams of orthocresol there was used 122 grams of 1.3.4 xylenol; instead of using 122 grams of para-ethylphenol there was used 164 grams of para-tertiaryamylphenol. and 250 grams oi xylene were used instead of 200 grams. The resultant resin on a solvent-free basis was hard, brittle, and reddish in color. It was not completely soluble in xylene but was reasonably soluble. The resin itself had a melting point of 180 to 185 C.

Example 135a The same procedure was followed as in Example 131a, except that the para-ethylphenol was replaced by a molar equivalent of para-nonylphenol. Speciflcally,122 grams of para-ethylphenol were replaced by 220 grams of para-nonylphenol. The amount of xylene was reduced from 200 grams to grams. The solvent-free resin was reddish amber in color, xylene-soluble, and soft or pliable in consistency.

Example 136a The same procedure was followed as in Example 131a, except that the para-ethylphenol was replaced by an equimolar amount of para-phenyl- Speciiically, 122 grams of para-ethylphenol were replaced by 170 grams of paraphenylphenol. The xylene was increased from 200 to 250 grams. and brittle, having a melting point of about lto C; It was reddish amber in color, and not particularly transparent. being somewhat opaque in appearance. It was not particularly soluble in xylene but dispersed sumciently for the purpose intended.`

Example 138a larly transparent. It was xylene dispersible to an extent sufficient for the purpose intended but not completely soluble. The solvent-free resin had a melting point of to 155 C.

' Example 139a The same procedure was followed as in Example 131a, except that the orthocresol was replaced by -an equal weight of paracresol and the 122 grams of paraethylphenol were replaced by 198 grams of para-phenylethylphenol (para-styrylphenol). 'I'he solvent-free resin obtained was hard, brittle, greenish-black in color, with a melting point of 130 to 135 C.

The resin obtained was hard 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE OXYALKYLATED SYNTHETIC RESIN; SAID SYNTHETIC RESIN BEING ONE IN WHICH THE RATIO OF OXYALKYLENE GROUP TO STRUCTURAL UNITS 